Charge density studies of multicentre two-electron bonding of an anion radical at non-ambient temperature and pressure

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Charge density studies of multicentre two-electron bonding of an anion radical at non-ambient temperature and pressure. / Milasinovic, Valentina; Molcanov, Kresimir; Krawczuk, Anna et al.

In: IUCrJ, Vol. 8, No. Pt 4, 01.07.2021, p. 644-654.

Research output: Contribution to journal › Article › peer-review

Author

Milasinovic, Valentina ; Molcanov, Kresimir ; Krawczuk, Anna et al. / Charge density studies of multicentre two-electron bonding of an anion radical at non-ambient temperature and pressure. In: IUCrJ. 2021 ; Vol. 8, No. Pt 4. pp. 644-654.

BibTeX

@article{f57ee9e75c64429298af802b7e438b03,

title = "Charge density studies of multicentre two-electron bonding of an anion radical at non-ambient temperature and pressure",

abstract = "The variation of charge density of two-electron multicentre bonding (pancake bonding) between semiquinone radicals with pressure and temperature was studied on a salt of 5,6-dichloro-2,3-dicyanosemiquinone radical anion (DDQ) with 4-cyano-N-methylpyridinium cation (4-CN) using the Transferable Aspheric Atom Model (TAAM) refinement. The pancake-bonded radical dimers are stacked by non-bonding π-interactions. With rising pressure, the covalent character of interactions between radicals increases, and above 2.55 GPa, the electron density indicates multicentric covalent interactions throughout the stack. The experimental charge densities were verified and corroborated by periodic DFT computations. The TAAM approach has been tested and validated for atomic resolution data measured at ambient pressure; this work shows this approach can also be applied to diffraction data obtained at pressures up to several gigapascals.",

keywords = "pi-stacking, non-aromatic rings, multicentre bonding, charge density, high pressure, EXPERIMENTAL ELECTRON-DENSITY, DATA-BANK, SMALL-MOLECULE, WAVE-FUNCTIONS, PI-STACKING, REFINEMENT, CRYSTALS, QUALITY, TRANSFERABILITY, PARAMETERS, non-Aromatic rings, π-stacking",

author = "Valentina Milasinovic and Kresimir Molcanov and Anna Krawczuk and Bogdanov, {Nikita E.} and Zakharov, {Boris A.} and Elena Boldyreva and Christian Jelsch and Biserka Kojic-Prodic",

note = "Publisher Copyright: {\textcopyright} 2021.",

year = "2021",

month = jul,

day = "1",

doi = "10.1107/S2052252521005273",

language = "English",

volume = "8",

pages = "644--654",

journal = "IUCrJ",

issn = "2052-2525",

publisher = "International Union of Crystallography",

number = "Pt 4",

}

RIS

TY - JOUR

T1 - Charge density studies of multicentre two-electron bonding of an anion radical at non-ambient temperature and pressure

AU - Milasinovic, Valentina

AU - Molcanov, Kresimir

AU - Krawczuk, Anna

AU - Bogdanov, Nikita E.

AU - Zakharov, Boris A.

AU - Boldyreva, Elena

AU - Jelsch, Christian

AU - Kojic-Prodic, Biserka

PY - 2021/7/1

Y1 - 2021/7/1

N2 - The variation of charge density of two-electron multicentre bonding (pancake bonding) between semiquinone radicals with pressure and temperature was studied on a salt of 5,6-dichloro-2,3-dicyanosemiquinone radical anion (DDQ) with 4-cyano-N-methylpyridinium cation (4-CN) using the Transferable Aspheric Atom Model (TAAM) refinement. The pancake-bonded radical dimers are stacked by non-bonding π-interactions. With rising pressure, the covalent character of interactions between radicals increases, and above 2.55 GPa, the electron density indicates multicentric covalent interactions throughout the stack. The experimental charge densities were verified and corroborated by periodic DFT computations. The TAAM approach has been tested and validated for atomic resolution data measured at ambient pressure; this work shows this approach can also be applied to diffraction data obtained at pressures up to several gigapascals.

AB - The variation of charge density of two-electron multicentre bonding (pancake bonding) between semiquinone radicals with pressure and temperature was studied on a salt of 5,6-dichloro-2,3-dicyanosemiquinone radical anion (DDQ) with 4-cyano-N-methylpyridinium cation (4-CN) using the Transferable Aspheric Atom Model (TAAM) refinement. The pancake-bonded radical dimers are stacked by non-bonding π-interactions. With rising pressure, the covalent character of interactions between radicals increases, and above 2.55 GPa, the electron density indicates multicentric covalent interactions throughout the stack. The experimental charge densities were verified and corroborated by periodic DFT computations. The TAAM approach has been tested and validated for atomic resolution data measured at ambient pressure; this work shows this approach can also be applied to diffraction data obtained at pressures up to several gigapascals.

KW - pi-stacking

KW - non-aromatic rings

KW - multicentre bonding

KW - charge density

KW - high pressure

KW - EXPERIMENTAL ELECTRON-DENSITY

KW - DATA-BANK

KW - SMALL-MOLECULE

KW - WAVE-FUNCTIONS

KW - PI-STACKING

KW - REFINEMENT

KW - CRYSTALS

KW - QUALITY

KW - TRANSFERABILITY

KW - PARAMETERS

KW - non-Aromatic rings

KW - π-stacking

UR - http://www.scopus.com/inward/record.url?scp=85130294988&partnerID=8YFLogxK

U2 - 10.1107/S2052252521005273

DO - 10.1107/S2052252521005273

M3 - Article

C2 - 34258012

VL - 8

SP - 644

EP - 654

JO - IUCrJ

JF - IUCrJ

SN - 2052-2525

IS - Pt 4

ER -

ID: 34690408